Treatment of human hair with zinc and cadmium dithiolate derivatives

ABSTRACT

Compositions for setting hair containing a bivalent metal dithiolate derivative having at least one N-methylol group and the process of treating human hair with these compositions.

United States Patent Bore 1451 July 4,1972

I [54] TREATMENT OF HUMAN HAIR WITH ZINC AND CADMIUM DITHIOLATE DERIVATIVES [72] Inventor: Pierre Bore, Montfermeil, France [73] Assignee: Societe Anonyme dite LOreal [22] Filed: Feb. 19, 1969 211 App]. No.: 800,721

[30] Foreign Application Priority Data Feb. 20, 1968 Luxembourg ..55,515

52 us. Cl .132/7, 81127.51, 117/119.6.

[56] References Cited UNITED STATES PATENTS 3,063,908 11/1962 Kalopissis ..424/7 2 X OTHER PUBLICATIONS Haefele et al., American Perfumer & Aromatics, Jan. 1960, pp. 39- 40, 42, 44- 46 and 48- 50 Primary Examiner-Albert T. Meyers Assistant Examiner-Vera C. Clarke Attorney-Holcombe, Wetherill and Brisebois 57 ABSTRACT Compositions for setting hair containing a bivalent metal dithiolate derivative having at least one N-methylol group and the process of treating human hair with these compositions.

9 Claims, No Drawings TREATMENT OF HUMAN HAIR WITH ZINC AND CADMIUM DITHIOLATE DERIVATIVES SUMMARY OF THE INVENTION Me represents a bivalent metal.

X, and X,, which may or may not be identical and may be omitted, have the following significances:

a. carbon-carbon bond,

b. substituted or unsubstituted, straight or branched chain aliphatic hydrocarbons having one to six carbon atoms, such as alkyl,

c. aryl chains, such as benzene,

d. --Z NR chains, in which 2 represents a substituted or unsubstituted, straight or branched chain hydrocarbon having one to six carbon atoms, such as alkyl, alkenyl, etc., R represents a hydrogen atom or hydrocarbon group, which may be substituted. (These substitutions may be of very different types, such as carboxyl, amine, etc.)

Y, and Y,, which may or may not be identical, represent a hydrogen atom or a hydroxyl group (in the case of free methylols), which may, in certain cases, be etherified, or converted by the Mannich reaction with a secondary amine, but only one of Y, and Y, may represent ahydrogen atom.

One may have, for example:

Y, H Y, OH (monomethylols) Y, Y, H (dirnethylols) Y, HY, OR

(in which R represents an alkyl radical having up to six carbon atoms.)

in accordance with the invention the bivalent metal may be selected from the group consisting of tin ll, chromium ll, nickel, manganese ll, cadmium, zinc, antimony ll, barium, strontium, calcium, magnesium, cobalt 11, iron ll, etc.

Among the compounds according to the invention which correspond to the above formula are: cadrniurl-bis-[N- hydroxymethyl-carbamoyl-methylthiolate] having the formu- S-CHz-CONII-CHzOH s-cm-oomr-omon -cadmlum-bls-[N'morphollnomethylureido-methylthlolate] having the formula:

mum-b15424 !-ruorphollnomethylureldo)ethylthlolate] having the orm a:

-cadmitun-bis-[2-mcthyoxycarbonyl-2-(N-morpholinomethylureido) ethylthlolate] having tho formula:

It is also an object of the present invention to provide a method of preparing the above-described new compounds, which method is characterized by the fact that a thiol having a function which can be converted to N-methylol is transformed by reacting it with a salt of a bivalent metal, and the resulting thiolate is transformed by reaction with formol into a rnethylol thiolate.

In a preferred embodiment of the invention the thiolate of I the thiol which can be transformed into N-methylol is precipitated by adding said thiol little by little to a solution of a bivalent metallic salt such as Zu,Cu,Cd,Ba,Sr,Ca salts.

In a particular embodiment of the invention the N-methylol group of said thiolate is esterified or subjected to a Mannich reaction.

The new compounds which have just been described have a bifunctional structure which imparts thereto properties which are particularly valuable in the cosmetic field.

These compositions have both a thiolate group and at least one methylol group, each of these groups having a reactivity with keratinic fiber which imparts particularly advantageous properties to the composition.

In fact, the reactivity and analytic behavior of the thiolates approach those of thiols, but they are not as readily oxidized as thiols. On the other hand, these compounds are more reactive than disulfides, and have the particular advantage of being able to form mixed disulfides by reacting with the keratocystine of the hair.

.Moreover, thanks to the presence of at least one l i c -pis-lN-hydmxymeth l-cubmo l-memynmoim having the forof keratm' the peculiarity that they Pdymndense themselves, while first forming oxymethylene bonds and then methylene bonds.

As a consequence of these particular properties, the new compounds which have just been described may be used for a wide variety of purposes in the cosmetic field.

On the one hand by reason of their double reactivity with keratocystine and the amine groups of basic amino-acids or of tyrosine, they have an extremely valuable reticulating effect on keratinic fiber.

On the other hand they are capable of supplying very bright transparent insoluble polymers, when heated under diflerent conditions in a medium having a pH greater than the pH at which the Me-S bond ruptures. This characteristic is particularly valuable in making setting lotions.

The invention relates to various methods of treating the hair, characterized by the fact that the hair is impregnated with compositions containing compounds according to formula l in proportions varying between 0.1 and percent by weight.

In a preferred method of carrying out the invention the neutralization step of a pennanent wave or a two-step permanent set is carried out by impregnating the hair, while it is rolled up on curlers, with a composition comprising at least one compound according to formula l at a concentration between 0.05 moles and 0.4 moles per liter, the pH of the composition being preferably alkaline and between 8 and 10.

The process according to the invention is particularly useful in fixing permanent sets.

in this process the hair is wound up on setting rollers of average diameter, after having been impregnated with a reducing solution, such as a solution of thiol utilized in permanent waving. The method of fixing the permanent set according to the invention is particularly advantageous in the present case because in order to fix the set it sufiices to apply a solution of the compound of formula to hair which has first been reduced and rinsed, and to dry the hair under a dryer without rinsing it. This results in excellent chemical fixation and an addition of polymers which results from the polymerization of the compounds according to formula 1.

ln accordance with the invention, a permanent hair set may be produced by following a new technique made possible by using thiolates according to the invention. This consists in treating the hair with a reducing solution without putting it up on curlers, rinsing it, impregnating it with a thiolate solution according to the invention, then winding the hair up on setting rollers, and finally drying the hair.

This produces excellent permanent sets, the quality of which results from the fact that the reconstitution of the disulfide bonds of the keratin takes place simultaneously with the formation of a resinous sheath on the hair.

In accordance with the invention, the compounds of formula I also make it possible to recondition hair which has been degraded as the result of bleaching, for example.

It is particularly well known that the thioglycolic acid used in permanent waving has an adverse effect on strongly bleached hair.

In accordance with the invention, the first step of a permanent waving process consists in applying to a head of hair which has been strongly bleached an aqueous solution, which is prepared at the moment of use, and contains a mixture of at least one compound according to formula l and ethylene diamine tetracetic acid, the pH of the solution being brought to between 8 and 10. The second step of this permanent waving process may be carried out in a conventional manner.

This process has, moreover, a particular advantage in that it makes it possible to prepare a permanent waving powder in a simple manner, since the thiolatei according to the invention keep much better when exposed to the air then conventional thiols do.

In the same field of protecting and restoring bleached hair, such hair may be protected from the adverse effects of permanent waving liquids by applying thereto a solution containing at least one compound according to formula I, and then drying the hair before permanently waving it in a conventional manner.

In accordance with the invention, bleached hair may be permanently set by impregnating it with a composition comprising at least one compound of formula I, and having a pH value and 10, after which the hair is rinsed and set in a conventional manner.

It is a further object of the present invention to provide a cosmetic composition adapted to be used in carrying out the above described processes, which composition is characterized by the fact that it comprises at least one compound according to formula I in a concentration between 0.1 and 20 percent and has a pH value between 7 and 10 and preferably between 8 and 10.

The compositions according to the invention may take the form of an aqueous solution, a cream, a gel or an aerosol, depending on which method of application is most appropriate to the end desired. They may also take the form'of a powder which is dissolved at the moment of use.

The compositions according to the invention may also contain' various active ingredients conventionally included in cosmefics such as swelling agents, surface-active agents, dyes, and perfumes. These various agents may be selected to suit the particular treatment which is to be carried out by means of the composition.

A further object of the present invention is to provide a method of coating metals characterized by the fact that a film of a solution containing at least one thiolate according to for mula l is applied to a metallic surface which has first been washed and degreased. The metallic surface is then left at the ambient temperature for a moment, after which it is put in an oven for from 1 to 48 hours until it sets to form a varnish type coating.

Among the metals and alloys which may be most advantageously coated in accordance with the invention are copper, brass and steel.

In order that the invention may be better understood, several examples showing the preparation of compounds according to the invention, and several examples showing how such compounds may be used will now be described, purely by way of illustration, without in any way suggesting that the scope of the invention is limited to the specific subject matter disclosed in said examples.

EXAMPLES OF THE PREPARATION OF COMPOUNDS ACCORDING TO THE INVENTION EXAMPLE 1 Preparation of cadmium-bis-[N-hydroxymethyl-carbamoylmethylthiolate] corresponding to the formula:

The starting reactant used in this preparation is thioacetamide, which may be obtained by aminolysis of ethyl thioglycolate.

The reaction producing the thiolate is the following:

agitated all the time this addition is being made. The result is a white precipitate which is easily decanted and can be filtered on fritted No. 2 glass. This precipitate is washed with 1 liter of water per 100 ml and dried after washing.

Finally, the precipitate is washed three times with 100 ml of 5 /SCH:CONH: ca 801120 C(l\ CHzO in excess SCII2CONIICII2OH 150 g of cadmium thiolate and 340 ml of 36 percent fonnol is mixed in a 500 ml Erlen flask. The mixture is heated to 80 C under constant agitation. At the end of 2 hours at 80 C the cadmium thiolate is completely dissolved.

The resulting solution is a little cloudy, and is filtered on No. 4 fritted glass.

It is then precipitated in 4.5 l of acetone at 0 C, which is continuously agitated while the methylol thiolate solution is introduced drop by drop. The precipitate is left to drain at room temperature for an hour, and the cloudy supernatant liquid is eliminated. The precipitate is filtered on fritted No. 4 glass.

The resulting product is washed with 3 liters of acetone in small fractions, the precipitate is malaxated and dried after each washing.

The resulting product is dried by spreading it out in thin layers and being left to stand for 3 to 4 days while exposed to the air.

The yield of the reaction is 95 percent.

A quantitative analysis of the various constituents of the resulting product was made, with the following results:

THEORETICAL FOUND SH l8.75% l7.80-l8.0

Cd 31.93% 3l.553 l .74

Free formol 0 Total Formol 17.04% l5.5l5.6

EXAMPLE ll Preparation of cadmium-bis-[Z-(N'-hydroxymethylureido)- ethylthiolate] having the formula:

In a first step, cysteamine cadmium thiolate is prepared by carrying out the following reaction:

In a second step, the corresponding ureide is prepared by the following process:

14.30 g of potassium isocyanate dissolved in 10 ml of water is added to the preceding solution and left standing for 2 hours. The solution is then precipitated by adding a 2N solution of sodium hydroxide and the result is a sticky nacreous mass which is washed with water. It is then purified by redissolving it in hot water and reprecipitated at 0 C. The precipitate is malaxated in acetone to produce a powder. A 65 percent yield of the ureide is obtained.

Elementary analysis of the resulting compound yields the following results:

SH 17.90% Theoretical: l8.83% N 13.52% Theoretical: 15.98% Cd 33.3 Theoretical: 32.0

filtered out and washed with water and acetone.

The yield of the reaction is 83 percent.

EXAMPLE Ill Preparation of cadmium-bis-[N-morpholinomethylcar- 'bamoylmethylthiolate] having the formula:

This composition is prepared by the following process:

, agitating vigorously. This is heated at 60 C until it dissolves.

The cadmium-bis-[carbamoyl-methylthiolate] is prepared as described in Example I.

29.2 g(0.l mole) of cadmium thiolate is mixed with 30 g (0.8 mole) of a commercial 40 percent fonnol solution and 34.8 g (0.8 mole) of morpholine.

The resulting mixture is heated while being agitated for 2 hours at 80 C. The cadmium thiolate dissolves. The mixture is left to cool at room temperature and then poured drop by drop into a liter of acetone at 0 C. The resulting precipitate is left to stand for about 2 hours at room temperature.

This precipitate is then filtered on fritted No. 2 glass and washed copiously with acetone, using 100 ml of acetone at a time. The product is then vacuum dried until the traces of acetone disappear.

The result is a 54 percent yield in the form of a white powder.

Analysis of the product obtained yields the following results:

THEORETICAL FOUND C 34.25% 31.68% H 5.25% 5.87% Nll.42% ll.l5% SH 13.48% l3.0% Cd 22.93% 28. I% CH,O 12.24% 11.5%

EXAMPLE IV Preparation of cadmium-bis-[2-(N'morpholinomethylu- 0 reido)-ethylthiolate].

This compound is prepared by the following process:

S(CHz)2-NHCONH2 Cysteamine cadmium thiolate and its ureide are prepared as described in Example I].

35 g ofureide is suspended in 100 ml ofwater. 15 g of40 percent formol and 17.4 g of morpholine are added while The water of the solution, which is quite viscous, is evaporated under vaeuum,in the presence of P,O,.

A solid white product is obtained after two days of vacuum drying. The yield is 93 percent.

Analysis of the resulting product yields the following results:

THEORE'HCAL FOUND s11 12.031, 1 1.8% N 15.31% 14.15% ca 20.49% 25.9%

EXAMPLES OF APPLICATIONS OF THE COMPOUNDS ACCORDING TO THE INVENTION EXAMPLE I The metallic surfaces were then found to be coated with a hard, adherent varnish.

This varnish may be very easily removed by means of dilute acid or a solution of ethylenediamine tetracetic acid.

EXAMPLE 2 A female head of leave human hair was sharnpooed, dried, rolled up on setting rollers of normal diameter while each lock is successively impregnated with a conventional permanent waving solution.

After the winding process is completed, the hair is again saturated and left for 10 to 20 minutes under a hood.

The hair is then rinsed again, and a 5 percent solution of a compound having the following formula, which is prepared at the moment of use, is applied to the hair, after being brought to Ph 9.5 by the addition of ammonia.

The hair is then immediately placed under a drier and dried in a conventional manner. It is removed from the rollers and combed.

An excellent chemical fixation results, which is comparable in quality to those obtained with conventional fixatives and is additionally characterized by a total absence of odor and a valuable increase in body" due to the polymerization of the methylol thiolate when heated under the hood.

After subsequent shampooings the wave holds well, thus demonstrating the eflectiveness of the chemical fixation.

EXAMPLE 3 A mixture of cadmium-bis-IN-hydroxymethyl-carbamoylmethylthiolate] and E.D.T.A. is dissolved in an ammonia solution at the moment of use. After mixing, the composition contains:

The above thiolate E.D.T.A.

Ammonia, q.s.p. pH 9.5 .Water, q.s.p. I00 cc This solution is applied to strongly bleached hair as if it were a conventional permanent waving solution. The head is covered by a hood. After 30 to 40 minutes the hair is rinsed, and fixed in a conventional manner with hydrogen peroxide. It is again rinsed and a permanent of good quality results. It has an attractive curl, body, and is in good condition.

EXAMPLE 4 One side of a head of previously bleached hair is treated with a 2 percent solution of cadmium-bis-[( N-hydroxymethylcarbamoyl-methylthiolate] having a pH of 8.3. It is then placed under a hood for several moments to dry the hair and polymerize the compound.

The entire head of hair is then given a permanent wave in a conventional manner by applying an ordinary commercial liquid having the following composition:

Thioglycolic acid 5% Ammonium sesquicarbona 4% Ammonia, q.s.p. pH 7.3

Water, q.s.p. I00 cc After the usual waiting period, the hair is rinsed, neutralized with a solution of hydrogen peroxide at 6 volumes, and again rinsed.

On the side which was impregnated with the thiolate the hair is in excellent condition, the curls are deep and round, the tips of the hair are in good condition. On the other side which represents the result of a conventional procedure, it was found that the hair was dry and rough, the wave was flat, and the hair less attractive in appearance.

EXAMPLE Strongly bleached hair was treated with a setting lotion comprising 2 percent of cadmium-bis-[N-hydroxymethyl-carbamoyl-methyl-thiolate] having a pH of 8.3 which may also comprise 3 percent of polyvinyl pyrrolidone, a conventional ingredient. The hair is wound up on setting rollers and dried. The rollers are then removed. The resulting wave has excellent holding power and the hair is in good condition.

EXAMPLE 6 A shampoo is prepared at the moment of use by mixing 5 g of cadmium-bis-[N-hydroxymethyl-carbamoyl-methylthiolate] with a solution containing:

Technical (30% )lauryl ether-sodium sulfate 25 g Laurie monoethanolamide 2 g Triethanolarnine q.s.p. pH 8.5

Water q.s.p. 100 cc EXAMPLE 7 After a head of hair has been shampooed and dried, it is reduced by a permanent waving liquid having an alkaline or neutral pH. Such a liquid may, for example, be a commercial permanent waving solution. After being left for a short time, preferably under a hood, the hair is rinsed and an aqueous solufion prepared at the moment of use is applied. This contains 5 or 10 percent of cadmium-bis-l N-hydroxymethyl-carbamoyl-methylthiolate and has a pH of 9.5. The hair is wound up on setting rollers, dried, and combed.

This process results in a long-lasting set, without any of the technical complications resulting from a conventional permanent setting process. The wave has better holding power, even though the moist hair shows practically no permanent waves.

When the composition according to the invention is a shampoo, the detergents can be alkyl sulfates alkyl ether sulfates, alkyl polyether sulfates, alkyl sulfonates, in which the alkyl groups have eight to 18 carbon atoms, sulfated monoglycerides, sulfonated monoglycerides, sulfated alkanolarnides, sulfonated alkanolamides, soaps of fatty acids, monosulfosuccinates of fatty alcohols, the products of the condensation of fatty acids with methyl-taurine, the products of the condensation of fatty acids with sarcosine, the products of the condensation of fatty acids with a protein hydrolysate; cationic detergents such as long chain quaternary ammonium, esters of fatty acids and of amine alcohols, polyether amines; non-ionic detergents such as the esters of polyols and sugars, the products of the condensation of ethylene oxide with fatty acids, fatty alcohols, long chain alkyl phenyls, long chain mercaptans, and long chain amides, the polyethers of polyhydroxylated fatty alcohols; or amphoteric detergents such as asparagine derivatives, the products of the condensation of monochloroacetic acid and irnadazolines, and alkyl arninopropionates.

Cosmetic carriers which can be utilized can be water-alcohol, gel, cream and aerosol.

The diflerence between a permanent wave and a permanent set consists in the fact:

In a permanent wave a the hairs are rolled on curlers of little diameter b. the hairs are rinsed with water after neutralization c. the hairs do not need to be dried on curlers after neutralization.

In a permanent set:

a. the hairs are rolled on rollers of middle diameter b. the hairs are not rinsed after neutralization c. the hairs are dried on the rollers.

What is claimed is:

l. A cosmetic composition for human hair comprising an aqueous solution of O. l-20 percent by weight of a compound having the formula wherein:

Me is selected from the group consisting of zinc and cadmiurn, X and X are selected from the group consisting of carboncarbon bond,

and

Y and Y, are selected from the group consisting of said composition having a pH of 8-10.

2. The composition of claim 1 wherein said compound is selected from the group consisting of cadmium-bis-[N- hydroxymethyl-carbarnoyl-methylthiolate], zinc-bis-[N- hydroxymethyl-carbamoyl-methylthiolate cadmium-bis-[ N morpholinomethylureido-methylthiolate] cadmium-bis-[ 2- (N '-hydroxymethylureido)-ethylthiolate] cadmium-bis-l 2( N -morpholinomethylurdeido )-ethylthiolate] cadmium-bis-( N morpholinomethyl-carbamoyl-methylthiolate) and cadmiumbis-I 2-methoxycarbonyl-2-( N '-morpholinomethylureido thyl-thiolate].

3. The composition of claim 1 ethylenediamine tetracetic acid.

4. A process for treating human hair comprising impregnating said hair with an eflective amount of a composition comprising an aqueous solution of 0.1-20 percent by weight of a compound having the formula also containing SCHzXzCONH-CH2Y:

wherein Me is selected from the group consisting of zinc and cadmiurn, X and X, are selected from the group consisting of carboncarbon bond,

.\'H, CHz-NH and -CHNH-- (:oocm and Y, and Y: are selected from the group consisting of OH and said composition having a pH of 8-l0.

5. The process of claim 4 which also includes winding said hair up on rollers prior to impregnating said hair with said composition.

6. The process of claim 4 which also includes prior to im pregnating said hair with said composition, impregnating said hair with a reducing solution and rinsing said hair and subsequent to impregnating said hair with said composition winding said hair up on rollers.

7. The process of claim 4 wherein said hair is bleached and which also includes subsequent to impregnating said hair with said composition, drying said hair at a temperature between 40-6O C and thereafter permanently waving said hair.

8. The process of claim 4 which also includes subsequent to impregnating said hair with said composition, winding said hair up on rollers and drying said hair at a temperature between 40-60 C.

9. The process of claim 4 wherein said composition also includes a detergent.

Patent No. 3,67 bO38 Pated July t, 1972 Inventor(s) Pierre Bore It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 6, delete lines 60-75 and insert therefor:

s-cH -com1 Cd 2HCOH QHN O s-c111 -co1m S-CH -CO-NH-CH -N o v 2 2 7 s-cH -co-NH-,-cH -N o Signed and sealed this 17th day of April 1973.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents F ORM Po-1050 (10-69) USCOMM-DC BOMB-P60 Q u s c-ovlmmlm unmuc. omcz nu O-MI-JJI 

2. The composition of claim 1 wherein said compound is selected from the group consisting of cadmium-bis-(N-hydroxymethyl-carbamoyl-methylthiolate), zinc-bis-(N-hydroxymethyl-carbamoyl-methylthiolate), cadmium-bis-(N''-morpholinomethyLureido-methylthiolate), cadmium-bis-(2-(N''-hydroxymethylureido)-ethylthiolate), cadmium-bis-(2(N''-morpholinomethylurdeido)-ethylthiolate), cadmium-bis-(N''-morpholinomethyl-carbamoyl-methylthiolate) and cadmium-bis-(2-methoxycarbonyl-2-(N''-morpholinomethylureido)-ethyl -thiolate).
 3. The composition of claim 1 also containing ethylenediamine tetracetic acid.
 4. A process for treating human hair comprising impregnating said hair with an effective amount of a composition comprising an aqueous solution of 0.1-20 percent by weight of a compound having the formula wherein Me is selected from the group consisting of zinc and cadmium, X1 and X2 are selected from the group consisting of carbon-carbon bond, and Y1 and Y2 are selected from the group consisting of -OH and said composition having a pH of 8-10.
 5. The process of claim 4 which also includes winding said hair up on rollers prior to impregnating said hair with said composition.
 6. The process of claim 4 which also includes prior to impregnating said hair with said composition, impregnating said hair with a reducing solution and rinsing said hair and subsequent to impregnating said hair with said composition winding said hair up on rollers.
 7. The process of claim 4 wherein said hair is bleached and which also includes subsequent to impregnating said hair with said composition, drying said hair at a temperature between 40*-60* C and thereafter permanently waving said hair.
 8. The process of claim 4 which also includes subsequent to impregnating said hair with said composition, winding said hair up on rollers and drying said hair at a temperature between 40*-60* C.
 9. The process of claim 4 wherein said composition also includes a detergent. 